Patent GB-1037241-A (GB)
Title: Process for preparing oil-soluble basic metal sulfonate compositions
IPC: C10M159/24
Filed: 1964-02-06
Abstract: A fuel or lubricating oil comprises a detergent additive obtained by carbonating a mixture of (A) one or more oil-soluble sulphonic acids, or a mixture of oil-soluble sulphonic and carboxylic acids, (B) an alcohol or mixture of alcohols, (C) an ammonium halide, an alkali metal halide, an alkaline earth metal halide or a mixture of such halides, and (D) an alkaline earth metal base or a mixture of such bases (see Division C2).  The concentration of basic metal compositions in the oil may range from 0.0001% to 30% by weight. More particularly, gasolines and fuel oils usually contain from about 0.001% to 0.5% by weight of the additive whereas greases, power transmitting fluids and lubricating oils may contain as much as 0.5% to 10% by weight of the additive.  Examples are given in which the additive is added to a light catalytically cracked petroleum fuel oil and to SAE20 mineral lubricating oil respectively.ALSO:Oil-soluble, basic metal compositions are prepared by carbonating a mixture containing:-(A) one or more oil-soluble sulphonic acids, or a mixture of oil-soluble sulphonic and carboxylic acids; (B) at least about 0.1 equivalent of an alcohol or a mixture of alcohols per equivalent of A; (C) from 0.1% to 5% by weight of (A) of an ammonium halide, an alkali metal halide, an alkaline earth metal halide or a mixture of such halides; (D) at least two equivalents per equivalent of (A) of an alkaline earth metal base or a mixture of such bases; at a temperature from 25 DEG  C. to the boiling point of the mixture containing (A), (B), (C) and (D).  Sulphonic acids suitable for use as component (A) may be aliphatic or aromatic and should preferably contain at least 12 aliphatic carbon atoms and specified acids are mahogany acid, monowax (eicosane)-substituted naphthalene sulphonic acid, dodecyl-, didodecyl-, dinonyl-sulphonic acids, octadecyl-diphenyl ether sulphonic acid, octadecyl - diphenylamine sulphonic acid, cetyl-chlorobenzene sulphonic acid, bis-cetylphenyl disulphide sulphonic acid, cetoxycapryl benzene sulphonic acid, dilauryl-beta-naphthalene sulphonic acid, nitronaphthalene sulphonic acid, paraffin wax sulphonic acid, bright stock sulphonic acids and cetyl-cyclopentane sulphonic acid. Carboxylic acids suitable for use in component (A) may be aliphatic or aromatic acids and specified acids are palmitic, stearic, myristic, oleic, linoleic, behenic, hexatriacontanoic, tetrapropylene substituted glutaric, octadecyl-substituted adipic, chlorostearic, 9-methyl stearic, dichlorostearic, stearyl benzoic, poly-wax (eicosane)-substituted naphthoic, dilauryl-decahydronaphthalene carboxylic, didodecyl-tetralin carboxylic, dioctyl-cyclohexane carboxylic acids and anhydrides of such acids.  The alcohols suitable for use as promoting agents, i.e. component (B) preferably contain up to 30 carbon atoms.  They may be monohydric or polyhydric alcohols, specified alcohols include nitropropanol, chloroethanol, aminoethanol, cinnamyl alcohol, allyl alcohol, benzyl alcohol and phenylethyl alcohol. Particularly useful are monohydric alcohols having up to 10 carbon atoms and mixtures of methanol with a higher monohydric alcohol in weight ratios from about 1:10 to 10:1. Suitable halides for use as component (C) are ammonium chloride, bromide and iodide; sodium chloride, bromide and iodide; potassium bromide and iodide, calcium chloride and bromide; and barium chloride. Hydrates of such halides are also useful.  It is convenient to introduce this component to the process mixture in the form of an aqueous solution or a slurry.  Suitable alkaline earth metal bases useful as component (D) include the oxides, hydroxides, bicarbonates, sulphides, mercaptides, hydrides, alcoholates and phenates of calcium, magnesium, barium and strontium.  Calcium oxide and hydroxide are preferred.  The presence of a small amount of water (up to 10% by weight) in the carbonation mixture is often advantageous. Carbonation may be accomplished by introducing CO2 into the reaction mixture.  After carbonation the alcoholic promoting agent may be removed by distillation if it is volatile, otherwise it may be left in the product.  The wate, if present, may also be removed by distillation.  The carbonation may also be carried out in other solvents such as n-hexane, naphtha, decane, dodecane, benzene, toluene, xylene, diphenylether chlorobenzene, or any other inert solvent. Examples are given in which (1) a neutral calcium bright stock sulphonate is carbonated in the presence of a mixture of methanol and iso-octyl alcohol as promotor ammonium chloride, calcium hydroxide as alkaline earth metal base and in the presence of toluene as solvent; (2) as in (1) except that calcium chloride replaces ammonium chloride; (3) as in (2) except that calcium hydroxide is added in four increments during carbonation; (4) the product of (3) is further carbonated in the presence of the same promoting agents and additionally lime (77% purity); (5) a mixture of neutral calcium bright stock sulphonate and distilled tall oil acid are carbonated in the presence of methanol, octanol and calcium chloride as promotors, calcium hydroxide as alkaline earth metal base and mineral oil as solvent; (6) as in (5); (7) as in (5) except that the tall oil acid is replaced by naphthenic acid, and (8) as in (1) except that mineral oil is used as solvent and calcium chloride is used in place of ammonium chloride.  The products are useful as additives for lubricating oils, gasolines, greases, cutting oils, transformer oils, burner fuel oils (see Division C5), and also for paints, plastics, resins, asphalts and power transmitting fluids.